JPH09152509A - Optical compensation sheet, element having polymer layer and element having oriented film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical compensation sheet which has excellent durability, exhibits a magnified visual field angle and is easily producible. SOLUTION: This optical compensation sheet is produced by providing the sheet with a transparent base 21, an oriented film 22 consisting of a polymer and an optical anisotropic layer 23 consisting of a liquid crystalline compd. in this order. In such a case, the polymer of the oriented film 23 and the liquid crystalline compd. of the optical anisotropic layer 23 are chemically bonded via the boundary of these layers. The element having this polymer layer is used for the formation of the optical compensation sheet and consists of a transparent base 21 and a polymer layer formed thereon. The polymer of the polymer layer described above consists of polyvinyl alcohol substd. in at least one hydroxyl group with a group having a vinyl part, oxysilanyl part or aziridinyl part.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical compensation sheet and an element that can be used for an optical element such as a liquid crystal cell of a liquid crystal display element, and an optical compensation sheet.

[0002]

2. Description of the Related Art A CRT (cathode ray tube) has been mainly used as a display device of OA equipment such as a desktop personal computer and a word processor. 2. Description of the Related Art Recently, liquid crystal display devices (hereinafter, referred to as LCDs) are widely used instead of CRTs because of their thinness, light weight, and low power consumption. An LCD generally includes a liquid crystal cell and a pair of polarizing plates provided on both sides thereof.

A liquid crystal cell is composed of a pair of transparent substrates provided with transparent electrodes and a liquid crystalline compound enclosed between them. The transparent substrate generally has an alignment film on the surface. The alignment film is formed by rubbing a layer of a polymer such as polyimide, polyvinyl alcohol or gelatin, or by obliquely depositing an inorganic compound. The alignment film has a function of defining the alignment direction of the liquid crystal compound. From the viewpoint of productivity, the alignment film is preferably a rubbing-treated polymer layer. For this reason, it has been earnestly desired to develop a polymer capable of easily and stably tilting and aligning a liquid crystal compound by rubbing.

Most of the LCDs having the above structure use twisted nematic liquid crystals. The LCD display system can be roughly classified into a birefringence mode and an optical rotation mode. Super twisted nematic liquid crystal display device utilizing birefringence mode (hereinafter STN-LC
(Referred to as D) uses a super-twisted nematic liquid crystal having a twist angle of more than 90 degrees and steep electro-optical characteristics. Therefore, such STN-LCD
Can display a large capacity by time division driving. However, STN-LCD has a slow response speed (several hundreds of milliseconds) and has a problem that gradation display is difficult. Therefore, a liquid crystal display device using active elements (eg, TFT-LCD and MIM-LCD) is used. Is inferior to the display characteristics of. TF
In T-LCDs and MIM-LCDs, twisted nematic liquid crystals with a twist angle of 90 degrees and positive birefringence are used for displaying images. TN-L
In the CD display mode, high-speed response (tens of milliseconds) and high contrast are obtained. Therefore, the rotation mode is
It has many advantages over birefringent modes and other modes. However, since the display color and the display contrast of the TN-LCD change depending on the angle at which the liquid crystal display device is viewed (viewing angle characteristic), the display characteristic does not reach the CRT level.

In order to improve the viewing angle characteristics (that is, to enlarge the viewing angle), it has been proposed to provide a retardation plate (optical compensation sheet) between a pair of polarizing plates and a liquid crystal cell. The retardation plate proposed does not exert any optical effect from the front directly because the retardation in the vertical direction to the liquid crystal cell is almost 0, but the retardation appears when it is tilted. This is to compensate for the phase difference that occurs in 1. This phase difference brings about unfavorable viewing angle characteristics such as coloring and disappearance of the displayed image. As such an optical compensation sheet, a sheet having negative birefringence so as to compensate for positive birefringence of a nematic liquid crystal and having an inclined optical axis is effective.

Japanese Unexamined Patent Publication No. 6-75115 discloses an optical compensation sheet having negative birefringence and having an inclined optical axis. That is, the sheet is manufactured by stretching a polymer such as polycarbonate or polyester, and has a direction of the main refractive index that is inclined from the normal line of the sheet. Since the production of the above-mentioned sheet by the stretching requires an extremely complicated stretching, it is extremely difficult to produce a large-area optical compensatory sheet by the disclosed method.

On the other hand, an optical compensation sheet using a liquid crystalline polymer is also known. For example, JP-A-3-9326 and JP-A-3-291601 disclose an optical compensation sheet obtained by coating a polymer having liquid crystallinity on the surface of an alignment film on a support film.
Polyimide is used as the polymer for the alignment film. As examples of other polymers, polyamides such as nylon (JP-A-3-9326) and polyvinyl alcohol (JP-A-3-291601) are also described. The polymers having liquid crystallinity described in these publications have a problem that they need to be aged at a high temperature for a long time in order to be oriented, and therefore have extremely low productivity and are not suitable for mass production. JP-A-5-215921 discloses an optical compensation sheet (birefringent plate) comprising a support, a polymerizable rod-like compound having liquid crystallinity and positive birefringence. This optical compensation sheet is obtained by coating a solution of a polymerizable rod-shaped compound on a support, orienting the compound in an electric field or a magnetic field, and then curing the compound. further,
This publication describes the use of a rubbing-treated polyimide film, a silane coupling agent layer having a long-chain alkyl group, and a vapor-deposited film of silicon oxide to orient the compound. Since the cured film having liquid crystallinity obtained above is optically uniaxially positive, the viewing angle in all directions can hardly be expanded.

[0008]

As described above, various polymers for the alignment film are known. However, in an alignment film obtained by rubbing a layer of these polymers, it is difficult to easily and stably tilt the liquid crystal compound. Therefore, the known optical compensation sheet including a support film, an alignment film, and a layer of a liquid crystalline compound cannot significantly expand the omnidirectional viewing angle.
The present applicant has already filed an application for an optical compensation sheet having a significantly wide viewing angle in all directions (Japanese Patent Application No. 6-11896).
No. 3). This optical compensatory sheet comprises a transparent support, an alignment film of a rubbing-treated polyvinyl alcohol provided thereon, and an optically anisotropic layer of a discotic liquid crystal compound formed on the alignment film. In this sheet, a wide viewing angle is obtained by using the discotic liquid crystalline compound. However, it cannot be said that the alignment film can easily and stably perform the tilted alignment of the discotic liquid crystalline compound. Furthermore, it has been found that the optical anisotropic layer sometimes peels from the alignment film when the optical compensation sheet is stored or used for a long period of time.

An object of the present invention is to provide an element having a polymer layer having a characteristic that a liquid crystal compound, particularly a discotic liquid crystal compound, can be easily aligned by subjecting the surface to an alignment treatment. To provide. Another object of the present invention is to provide an optical compensatory sheet having an alignment film capable of easily aligning a liquid crystal compound, particularly a discotic liquid crystal compound. Further, it is an object of the present invention to provide a method for producing an optical compensation sheet, which allows the optical compensation sheet to be easily produced with a high yield. Another object of the present invention is to provide an optical compensation sheet having excellent durability, exhibiting a wide viewing angle, and easily manufactured.

[0010]

The present invention provides a transparent support,
In an optical compensation sheet in which an alignment film made of a polymer and an optically anisotropic layer made of a liquid crystalline compound are provided in this order, the polymer of the alignment film and the liquid crystalline compound of the optically anisotropic layer form an interface between these layers. The optical compensatory sheet is characterized in that it is chemically bonded via. Preferred embodiments of the optical compensation sheet of the present invention are as follows. 1) The polymer of the alignment film is formed of polyvinyl alcohol in which at least one hydroxyl group is substituted with a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety. 2) The optically anisotropic layer is formed of a liquid crystal compound having a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety. 3) The liquid crystalline compound of the optically anisotropic layer is a discotic liquid crystalline compound having a group having a vinyl portion, an oxiranyl portion or an aziridinyl portion.

The present invention also resides in an element having an alignment film having the structure of the above optical compensation sheet.

The element having the above-mentioned optical compensation sheet or alignment film can be advantageously obtained by using the element having the polymer layer of the present invention described below. A transparent support and a polymer layer provided thereon, wherein the polymer of the polymer layer is polyvinyl alcohol in which at least one hydroxyl group is substituted with a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety. An element having a polymer layer characterized in that However, the above vinyl moiety, oxiranyl moiety or aziridinyl moiety includes respective lower alkyl substituents. Preferred embodiments of the element having the polymer layer of the present invention are as follows. 1) A group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety is bonded to a polymer chain of a polyvinyl alcohol derivative via an ether bond, a urethane bond, an acetal bond or an ester bond. 2) A group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety does not have an aromatic ring. 3) The polyvinyl alcohol has the following general formula (I):

[0013]

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(However, L ¹¹ represents an ether bond, a urethane bond, an acetal bond or an ester bond; R 11
¹¹ represents an alkylene group or an alkyleneoxy group; L ¹² represents a linking group connecting R ¹¹ and Q ¹¹ ; Q
¹¹ represents vinyl, oxiranyl or aziridinyl; x1 is 10 under the condition of x1 + y1 + z1 = 100.
˜99.9 mol%, y1 is 0.01 to 80 mol%, and z1 is 0 to 70 mol%; and k and h are 0 or 1 respectively). 4) In general formula (I), R ¹¹ is —R ² — or —
_{^{R 3 - (O-CH 2}} CH 2) t - ( where, R ² and R ³ is an alkylene group and t 1 to 12 carbon atoms respectively 0-2
Is an integer. ) (In particular, R ¹¹ has 1 carbon atom)
~ 12 alkylene groups are preferred); and L ¹² is-
O-, -S-, -CO-, -O-CO-, -CO-O
-, -O-CO-O-, -CO-O-CO-, -NRC
O-, -CONR-, -NR-, -NRCONR-,-
NRCO-O- or -OCONR- (wherein R represents a hydrogen atom or a lower alkyl group), the above 3)
Element.

5) The polyvinyl alcohol has the following general formula (III):

[0016]

[Chemical 6]

(However, L ³¹ represents an ether bond, a urethane bond, an acetal bond or an ester bond;
³¹ represents an arylene group having 6 to 24 carbon atoms, or an arylene group having 6 to 24 carbon atoms substituted with halogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms; R ^31, -R ² - or -R ³
_{- (O-CH 2 CH 2} ) t - ( where, R ² and R ³ is an alkylene group and t having 1 to 12 carbon atoms each is an integer of 0 to 2.) The expressed; L ³² is -O-, -S-, -C
O-, -O-CO-, -CO-O-, -O-CO-O
-, -CO-O-CO-, -NRCO-, -CONR
-, - NR -, - NRCONR -, - NRCO-O- or -OCONR- (where, R represents a hydrogen atom or a lower alkyl group) Q ³¹ are vinyl, represents oxiranyl or aziridinyl; x2 + y2 + z2 = 100 conditions And x2 is 1
0-99.9 mol%, y2 is 0.01-80 mol%, and z2 is 0-70 mol%; and k1 and h1.
Are 0 or 1 respectively). 6) Polyvinyl alcohol has a repeating unit having a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety in a range of 0.1 to 10 mol% of all repeating units.

Further, the present invention is an optical compensation sheet comprising a transparent support, an alignment film made of a polymer, and an optically anisotropic layer made of a liquid crystalline compound in this order. An optical compensatory sheet comprising polyvinyl alcohol in which at least one hydroxyl group is substituted with a group represented by (II). Preferred embodiments of the optical compensation sheet of the present invention are as follows. 1) The liquid crystal compound of the optically anisotropic layer is a discotic liquid crystal compound. 2) The liquid crystalline compound of the optically anisotropic layer is a discotic liquid crystalline compound having a group having a vinyl portion, an oxiranyl portion or an aziridinyl portion.

The present invention also resides in an element having an alignment film having the structure of the above optical compensation sheet.

The element having the above optical compensation sheet or alignment film can be advantageously obtained by using the element having the polymer layer of the present invention described below. It comprises a transparent support and a polymer layer provided thereon, and the polymer of the polymer layer has the following general formula (II):

[0021]

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(Wherein R ²¹ represents an alkyl group or an alkyl group substituted with alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy; W ²¹ represents Alkyl group, alkyl,
Alkyl group, alkoxy group or alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyl substituted with alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy. An alkoxy group substituted with oxy or crotonoyloxy; q is 0 or 1; and n is an integer of 0 to 4) from polyvinyl alcohol substituted with at least one hydroxyl group. An element having a polymer layer characterized in that

Preferred embodiments of the element having the polymer layer of the present invention are as follows. 1) R ²¹ is an alkyl group, alkyl, alkoxy,
Represents an alkyl group substituted with aryl or halogen; and W ²¹ represents an alkyl group, alkyl, alkoxy, alkyl group substituted with aryl or halogen, alkoxy group, or alkoxy substituted with alkyl, alkoxy, aryl or halogen Represents a group. 2) R ²¹ represents an alkyl group substituted with vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy; and W ²¹ represents an alkyl group, alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, Oxiranyl,
Acryloyloxy, methacryloyloxy or crotonoyloxy substituted alkyl group, alkoxy group, or alkyl, alkoxy, aryl, halogen,
It represents an alkoxy group substituted with vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy. 3) Polyvinyl alcohol has a repeating unit having a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety in a range of 0.1 to 10 mol% of all repeating units. In the compound used in the present invention, there is no problem even if the hydrogen atom in the compound is a deuterium atom.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The element having a polymer layer of the present invention comprises a transparent support and a polymer layer comprising a specific polymer. A typical configuration of the above elements is shown in FIG. In FIG. 1, a polymer layer 12 is provided on a transparent support 11 and constitutes an element having a polymer layer. By subjecting the surface of the polymer layer 12 to an alignment treatment such as a rubbing treatment, the liquid crystal compound can be easily aligned. The polymer of the polymer layer is a polymerizable group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety,
Alternatively, it is a specific polymer having an aryl group. Preferred polymers have the general formula (I), (II) or (III)
Specific polyvinyl alcohol (However, (II)
Is represented only by that particular group).

The optical compensation sheet of the present invention comprises a transparent support,
It comprises an alignment film provided thereon and an optically anisotropic layer provided on the alignment film. A typical configuration of the above elements is shown in FIG. In FIG. 2, a transparent support 21, an alignment film 22, and an optically anisotropic layer 23, which is a layer of a liquid crystal compound, are provided in this order to form an optical compensation sheet. Alignment film 22
Is a layer obtained by subjecting the polymer layer of FIG. 1 to orientation treatment. The optical compensation sheet of the present invention is characterized in that the polymer of the alignment film 22 and the liquid crystal compound of the optically anisotropic layer 23 are chemically bonded via the interface between these layers. Such a chemical bond between the two layers is generally formed by a reaction between the polymerizable group of the polymer and the polymerizable group of the liquid crystal compound. In this case, the optically anisotropic layer is preferably a discotic liquid crystal compound having negative birefringence. Alternatively, the alignment film (or polymer layer) may be made of polyvinyl alcohol having no polymerizable group and having an aryl group capable of easily aligning the liquid crystal compound.

As the material of the transparent support of the present invention, any material can be used as long as it is transparent.
A material having a light transmittance of 80% or more is preferable, and a material having optical isotropy when viewed from the front is particularly preferable.
Therefore, the transparent support is preferably manufactured from a material having a small intrinsic birefringence. Examples of such materials include Zeonex (manufactured by Nippon Zeon Co., Ltd.) and ARTON.
Commercially available products such as (manufactured by Nippon Synthetic Rubber Co., Ltd.) and Fujitac (manufactured by Fuji Photo Film Co., Ltd.) can be used. Furthermore, even a material having a large intrinsic birefringence such as polycarbonate, polyarylate, polysulfone, and polyethersulfone can be obtained by appropriately setting conditions such as solution casting and melt extrusion.

When the main refractive index in the plane of the transparent support (film) is nx, ny, the main refractive index in the thickness direction is nz, and the film thickness is d, the relationship of the triaxial main refractive indexes is nz < ny
= Nx (negative uniaxiality), and the formula ｛(nx + ny) /
The retardation represented by 2-nz｝ × d is 20 nm
To 400 nm (preferably 30 to 150 nm). However, the values of nx and ny do not need to be exactly equal, but it is sufficient if they are approximately equal. In particular,
If | nx-ny | / | nx-nz | ≦ 0.2, there is no practical problem. The front retardation represented by | nx-ny | × d is preferably 50 nm or less,
More preferably, it is 20 nm or less.

An undercoat layer is preferably provided on the transparent support in order to increase the adhesive strength between the transparent support and the alignment film. Generally gelatin is used.

The alignment film of the present invention is provided on a transparent support. The alignment film has a function of defining an alignment direction of a liquid crystal compound such as a discotic liquid crystal compound provided thereon by coating or the like, and the alignment gives an optical axis tilted from the optical compensation sheet. In the present invention, the alignment film is a polymer layer that has been subjected to alignment treatment such as rubbing treatment, and the polymer has a group having vinyl, oxiranyl, aziridinyl or aryl. The polymer is preferably polyvinyl alcohol. The alignment film will be described below by taking polyvinyl alcohol as an example. In the polyvinyl alcohol of the present invention, at least one hydroxyl group thereof is substituted with a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety. The above moiety is generally a polymer chain (carbon atom) of polyvinyl alcohol.
And an ether bond (-O-), a urethane bond (-OCO
NH-), acetal bond ((-O-) ₂ CH-) or an ester bond (-OCO -) [i.e., bonded radical linked via a. Urethane bond, acetal bond or ester bond is preferred. Vinyl, oxiranyl, aziridinyl or aryl is preferably indirectly bonded to polyvinyl alcohol via the above bond,
That is, it is preferable that the group having the above-mentioned moiety is bonded to polyvinyl alcohol together with the bonding group as described below.

The polyvinyl alcohol of the present invention is generally represented by the following general formula (I), (II) or (III) (provided that (II) represents only its group).

[0031]

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(However, L ¹¹ represents an ether bond, a urethane bond, an acetal bond or an ester bond; R 11
¹¹ represents an alkylene group or an alkyleneoxy group; L ¹² represents a linking group connecting R ¹¹ and Q ¹¹ ; Q
¹¹ represents vinyl, oxiranyl or aziridinyl; x1 is 10 under the condition of x1 + y1 + z1 = 100.
˜99.9 mol%, y1 is 0.01 to 80 mol%, and z1 is 0 to 70 mol%; and k and h are 0 or 1 respectively).

In the general formula (I), R ¹¹ is generally an alkylene group having 1 to 24 carbon atoms, and at least one non-adjacent CH ₂ group is —O—, —CO—, —NH—, —N.
R ⁷ - (R ⁷ represents an alkyl or aryl having 6 to 15 carbon atoms having 1 to 4 carbon atoms), - S -, - SO
₂ -or an alkylene group having 3 to 24 carbon atoms replaced by an arylene having 6 to 15 carbon atoms, or alkyl, aryl, alkoxy, aryloxy, alkylthio, arylthio, halogen, alkylcarbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl , Hydroxyl, mercapto, amino, alkylcarbonyloxy, arylcarbonyloxy, alkylsulfonyloxy, arylsulfonyloxy, alkylcarbonylthio, arylcarbonylthio, alkylsulfonylthio, arylsulfonylthio, alkylcarbonylamino, arylcarbonylamino, alkylsulfonylamino , Arylsulfonylamino, carboxy or any of the above alkylene groups substituted with sulfo.

R ¹¹ is --R ^2- , --R ^3- (OR ⁴ )
_{^{t -OR 5 -, - R 3}} -CO-R 6 -, - R 3 -NH-
^{R 6 -, - R 3 -NR} 7 -R 6 -, - R 3 -S-R 6
_{^{-, - R 3 -SO 2 -R}} 6 - or -R ³ -A ² -R ⁶ -
^{(Wherein, R 2, R 3, R} 4, R 5 and R ⁶ each represents an alkylene carbon atoms 1 to 24, R ⁷ is C6-15 alkyl or carbon atom having 1 to 12 carbon atoms And A ² represents arylene having 6 to 24 carbon atoms, and t represents an integer of 0 to 4). Further, R ¹¹ is —R ² — or —R ³ — (O—CH ₂ CH ₂ ) _t — (wherein R ² and R ³ are each alkylene having 1 to 12 carbon atoms, and t is 0 to 0).
It is an integer of 2. ) Is preferred, especially R ¹¹
Is preferably an alkylene having 1 to 12 carbon atoms.

The alkylene group may have a substituent. Examples thereof include alkyl having 1 to 24 carbon atoms, aryl having 6 to 24 carbon atoms, and 1 to 2 carbon atoms.
4 alkoxy, 6 to 24 carbon atom aryloxy, 1 to 24 carbon atom alkylthio, 6 carbon atoms
To 24 arylthio, halogen (F, Cl, Br),
Alkylcarbonyl having 2 to 24 carbon atoms, arylcarbonyl having 7 to 24 carbon atoms, alkylsulfonyl having 1 to 24 carbon atoms, arylsulfonyl having 6 to 24 carbon atoms, hydroxyl, mercapto, amino, having 2 carbon atoms Alkylcarbonyloxy having 24 to 24 carbon atoms, arylcarbonyloxy having 7 to 24 carbon atoms, and having 1 carbon atom
24 alkylsulfonyloxys having 6 to 24 carbon atoms
Arylsulfonyloxy, alkylcarbonylthio having 2 to 24 carbon atoms, arylcarbonylthio having 7 to 24 carbon atoms, alkylsulfonylthio having 1 to 24 carbon atoms, arylsulfonylthio having 6 to 24 carbon atoms, carbon Alkylcarbonylamino having 2 to 24 atoms,
Examples thereof include arylcarbonylamino having 7 to 24 carbon atoms, alkylsulfonylamino having 1 to 24 carbon atoms, arylsulfonylamino having 6 to 24 carbon atoms, carboxy and sulfo.

Preferred substituents on the alkylene group are alkyl having 1 to 24 carbon atoms (especially 1 carbon atom).
To 12), aryl having 6 to 24 carbon atoms (particularly 6 to 14 carbon atoms), and alkoxyalkyl having 2 to 24 carbon atoms (particularly 2 to 12 carbon atoms). Examples of alkyl include methyl, ethyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n
-Nonyl, n-decyl, n-undecyl, n-dodecyl, i-propyl, i-butyl, sec-butyl, t-
Amyl and 2-ethylhexyl can be mentioned.
Examples of alkyl substituted with 1 to 4 alkoxy include 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl, 2- [2- (2-methoxyethoxy) ethoxy] ethyl, 2-n-. Mention may be made of butoxyethyl, 2-ethoxyethyl, 2- (2-ethoxyethoxy) ethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propyloxypropyl and 2-methylbutyloxymethyl. Examples of aryl include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2-anisyl, 3-anisyl, 4-anisyl, 2-biphenyl,
-Biphenyl, 4-biphenyl, 2-chlorophenyl,
Examples include 3-chlorophenyl, 4-chlorophenyl, 1-naphthyl and 2-naphthyl. Examples of the heterocyclic group include pyridyl, pyrimidyl, thiazolyl, and oxazolyl.

L ¹² is --O--, --S--, --CO--, --O.
-CO-, -CO-O-, -O-CO-O-, -CO-
O-CO-, -NRCO-, -CONR-, -NR-,
-NRCONR-, -NRCO-O- or -OCON
R- (wherein R represents a hydrogen atom or a lower alkyl group)
Is preferably represented. - (L ¹²⁾ _h -Q ¹² are vinyl, vinyloxy, acryloyl, methacryloyl, crotonoyl, acryloyloxy, methacryloyloxy, crotonoyloxy oxy, vinyl phenoxy, vinyl benzoyloxy, styryl, 1,2-epoxy ethyl,
It is preferably 1,2-epoxypropyl, 2,3-epoxypropyl, 1,2-iminoethyl, 1,2-iminopropyl or 2,3-iminopropyl. Further, vinyl, vinyloxy, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, crotonoyloxy, vinylbenzoyloxy, 1,2-
Epoxy ethyl, 1,2-epoxy propyl, 2,3-
Epoxypropyl, 1,2-iminoethyl, 1,2-iminopropyl or 2,3-iminopropyl are preferred.
Particularly, acryloyl, methacryloyl, acryloyloxy and methacryloyloxy are preferred.

Under the condition of x1 + y1 + z1 = 100, x
1 is preferably 50 to 99.9 mol% and y1 is 0.01
To 50 mol% (more preferably 0.01 to 20 mol%)
Is preferable, and particularly 0.01 to 10 mol%, most preferably 0.01 to 5 mol%), and z1 is preferably 0.01 to 50 mol%.

When L ¹¹ is an acetal bond in the above general formula (I), the polyvinyl alcohol of the general formula (I) can be represented by the following general formula (Ia).

[0040]

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(However, L ¹¹ , R ¹¹ , L ¹² , Q ¹¹ , x1,
y1, z1, k and h have the same meanings as in the general formula (I). )

The polyvinyl alcohol of the present invention can also be represented by the following general formula (III).

[0043]

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(However, L ³¹ represents an ether bond, a urethane bond, an acetal bond or an ester bond;
³¹ represents an arylene group, or an arylene group substituted with halogen, alkyl, alkoxy or substituted alkoxy (as a substituent of the substituted alkoxy, alkoxy, aryl, halogen, vinyl, vinyloxy, acryloyl, methacryloyl, crotonoyl, Acryloyloxy, methacryloyloxy, crotonoyloxy, vinylphenoxy, vinylbenzoyloxy, styryl, 1,2-epoxyethyl, 1,2-epoxypropyl, 2,3-epoxypropyl, 1,2-iminoethyl, 1,2- Iminopropyl or 2,3-iminopropyl); R ³¹ represents the same group as R ¹¹ ; L ³² represents the same group as L ¹² ; Q ³¹ represents Q
Represents the same group as ¹¹ ; under the condition of x2 + y2 + z2 = 100, x2 is 10 to 99.9 mol% and y2 is 0.01
˜80 mol%, and z2 is 0 to 70 mol%; and k1 and h1 are each 0 or 1) In particular, A ³¹ is an arylene group having 6 to 24 carbon atoms, or a halogen atom or a carbon atom number. 6 to 6 carbon atoms substituted with 1 to 4 alkyl or 1 to 4 carbon alkoxy
It is preferably 24 arylene groups.

[0045] In group A ^31, carbon atoms arylene group is generally 6-24 carbon atoms, 6-12 are preferred. Examples of the arylene group include 1,4-phenylene,
1,3-phenylene, 1,2-phenylene and 1,5-phenylene
Naphthylene can be mentioned, and 1,4-phenylene is particularly preferable. Examples of the substituent of the arylene group include a halogen atom (F, Cl, Br or I), an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. Aryl having 6 to 15 carbon atoms, halogen, vinyl, vinyloxy, oxiranyl (1,2-epoxyethyl, 1,2-epoxypropyl, 2,3-epoxypropyl), aziridinyl (1,2-iminoethyl, 1,2 -Iminopropyl or 2,3-iminopropyl), acryloyl, methacryloyl, crotonoyl, acryloyloxy, methacryloyloxy, crotonoyloxy, vinylphenoxy,
Examples thereof include an alkoxy group having 1 to 4 carbon atoms and substituted with vinylbenzoyloxy or styryl.
It is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and particularly preferably F, Cl or methyl. x2 + y2 + z2 =
Under the condition of 100, x2 is preferably 50 to 99.9 mol%, y2 is preferably 0.01 to 50 mol% (particularly 0.01 to 20 mol%, particularly 0.01 to 10 mol%).
Mol%, most preferably 0.01-5 mol%) and z2.
Is preferably 0.01 to 50 mol%.

When L ³¹ is an acetal bond in the above general formula (III), the polyvinyl alcohol of the general formula (III) can be represented by the following general formula (IIIa).

[0047]

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(However, A ³¹ , R ³¹ , L ³² , Q ³¹ , x2,
y2, z2, k1 and h1 have the same meaning as in formula (III). )

Further, the polyvinyl alcohol of the present invention comprises
It is preferable that at least one hydroxyl group thereof is substituted with a group of the following general formula (II).

[0050]

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(Wherein R ²¹ represents an alkyl group or an alkyl group substituted with alkyl, alkoxy, allyl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy; W ²¹ represents Alkyl group, alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy substituted alkyl group, alkoxy group, or alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl Represents an alkoxy group substituted with acryloyloxy, methacryloyloxy or crotonoyloxy; q is 0 or 1, and n is an integer of 0 to 4 (preferably 0). Is 1, especially 0))

R ²¹ represents an alkyl group or an alkyl group substituted with alkyl, alkoxy, aryl or halogen; and W ²¹ represents an alkyl group, alkyl,
Alkyl group substituted with alkoxy, aryl or halogen, an alkoxy group, or alkyl, alkoxy,
It is preferred to represent an alkoxy group substituted with allyl or halogen.

R ²¹ represents an alkyl group substituted with vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy; and W ²¹ represents an alkyl group, alkyl, alkoxy, aryl, halogen, vinyl. , Vinyloxy,
Oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy substituted alkyl group, alkoxy group, or alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl,
It is preferably an alkoxy group substituted with acryloyloxy, methacryloyloxy or crotonoyloxy.

The number of carbon atoms in the above alkyl group or alkoxy group is preferably 1 to 24, particularly preferably 1 to 12. Examples of the alkyl group include an unsubstituted alkyl group (eg, methyl, ethyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n- Dodecyl, i-propyl,
i-butyl, sec-butyl, t-amyl and 2-ethylhexyl); an alkyl group substituted with 1 to 4 alkoxy (eg, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl, 2- [2 -(2-Methoxyethoxy) ethoxy] ethyl, 2-n-butoxyethyl, 2-
Ethoxyethyl, 2- (2-ethoxyethoxy) ethyl, 3-methoxypropyl, 3-ethoxypropyl,
-N-propyloxypropyl, 3-benzyloxypropyl and 2-methylbutyloxymethyl); aralkyl groups (eg 2-phenylethyl and 2- (4-
n-butyloxyphenyl) ethyl); vinylalkyl group (for example, vinylmethyl, 2-vinylethyl, 5-vinylpentyl, 6-vinylhexyl, 7-vinylheptyl and 8-vinyloctyl); vinyloxyalkyl group (for example, 2-vinyloxyethyl, 5-vinyloxypentyl, 6-vinyloxyhexyl, 7-vinyloxyheptyl and 8-vinyloxyoctyl); oxiranylalkyl groups (eg 3,4-epoxybutyl,
4,5-epoxypentyl, 5,6-epoxyhexyl, 6,7-epoxyheptyl, 7,8-epoxyoctyl and 6,7-epoxyoctyl); acryloyloxyalkyl group (for example, 2-acryloyloxyethyl, 3 -Acryloyloxypropyl, 4-acryloyloxybutyl, 5-acryloyloxypentyl,
6-acryloyloxyhexyl, 7-acryloyloxyheptyl and 8-acryloyloxyoctyl); methacryloyloxyalkyl groups (eg 2-
Methacryloyloxyethyl, 3-methacryloyloxypropyl, 4-methacryloyloxybutyl, 5-methacryloyloxypentyl, 6-methacryloyloxyhexyl, 7-methacryloyloxyheptyl and 8-methacryloyloxyoctyl); and crotonoyloxyalkyl groups (for example, 2 -Crotonoyloxyethyl, 3-crotonoyloxypropyl, 4-crotonoyloxybutyl, 5-crotonoyloxypentyl, 6
-Crotonoyloxyhexyl, 7-crotonoyloxyheptyl and 8-crotonoyloxyoctyl).

The substitution position of OR ^{21 with} the benzene ring is preferably the 3 or 4 position. The polyvinyl alcohol having a group of the general formula (II) has a repeating unit having a group of the general formula (II) in the range of 0.1 to 10 mol% of all repeating units (particularly 0.1 to 5 mol%). The range) is preferable.

The group of the general formula (II) has the following general formula (II
It can be introduced into polyvinyl alcohol by reacting a carboxylic acid derivative having a group of a) with polyvinyl alcohol,

[0057]

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In the general formula (IIa), R ²¹ , W ²¹ , n
And q are as defined in general formula (II), and X
Is necessary to form a carboxylic acid site activated form (X-
CO- can be activated). The group represented by X is described in, for example, "Peptide Synthesis (Chapter 5, Maruzen 1975)" by Nobuo Izumiya. For example, when an active ester is formed, examples of X include 4-nitrophenoxy and N-oxysuccinimide. In the case of forming an acid anhydride, a symmetrical acid anhydride and a mixed acid anhydride can be mentioned. As X in the case of the mixed acid anhydride, for example, methanesulfonyloxy, trifluoroacetyloxy, ethyloxy Carbonyloxy can be mentioned. X in the case of an acid halide includes, for example, a chlorine atom and a bromine atom. These compounds having the atom group represented by X do not necessarily need to be isolated, and those generated in the reaction system may be used as they are. As the carboxylic acid derivative, mixed acid anhydrides and acid halides are preferable, and methanesulfonyloxy type mixed acid anhydrides and acid chlorides are particularly preferable.

An example of the compound of the general formula (IIa) when X is OH (that is, the acid form) is shown below.

[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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In the present invention, the substituent introduced into the polymer chain (carbon atom) of polyvinyl alcohol is
Particularly, a substituent represented by the following general formula (IV) is preferable.

[0068]

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In the general formula (IV), L ⁴¹ represents an atom group necessary for forming a urethane bond, an acetal bond or an ester bond, and R ⁴¹ represents a vinyl, acryloyl, methacryloyl, crotonoyl group, styryl, oxiranyl or aziridinyl. Represents (especially acryloyl or methacryloyl), j and e are 0 or 1 respectively.
And d represents an integer of 2 to 24 (particularly 2 to 10).
And u represents an integer of 0 to 4.

A compound having a group to be introduced into polyvinyl alcohol or modified polyvinyl alcohol (eg, the above-mentioned general formula (IIa)) is reacted with polyvinyl alcohol to obtain polyvinyl alcohol having a specific group of the present invention. be able to. The polyvinyl alcohol or modified polyvinyl alcohol used for the reaction with the compound having the above specific group generally has a saponification degree of 70 to 10
It is 0%. Examples thereof include unmodified polyvinyl alcohol, copolymer-modified polyvinyl alcohol (as the modifying group, for example, -COONa, -S
_{i (OH) 3, -N (} CH 3) 3 · Cl, -C 9 H 19 C
OO, and it is introduced -SO ₃ Na or -C ₁₂ H _25, etc.), as modified polyvinyl alcohol (modified group by chain transfer, for example, -COONa, -SH or C ₁₂ H ₂₅ S- and the like introduced And a polyvinyl alcohol modified by block polymerization (as a modifying group, for example, —COOH, —CONH ₂ , —COOR
(R: alkyl) or —C ₆ H ₅ or the like is introduced). The degree of polymerization is 100 to
Those having a range of 3000 are preferred. Saponification degree is 80-1
A range of 00% is preferable, and a saponification degree of 85 to 95% is particularly preferable. The degree of polymerization is preferably in the range of 100 to 3000.

Examples of the polyvinyl alcohol of the present invention are shown below.

[0072]

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In the above general formula V-1, x, y and z
Is shown below. ──────────────────────────────────── x yz (mol%) (mol%) (mol% ) ──────────────────────────────────── Polymer No. 1 86.3 1.7 12 Polymer No. 2 85.0 3.0 12 Polymer No. 3 87.7 0.3 12 Polymer No. 4 70.0 18.0 12 Polymer No. 5 86.9 1.1 12 Polymer No. 6 98.5 0.5 1 Polymer No. 7 97.8 0.2 2 Polymer No. 8 96.5 2.5 1 Polymer No. 9 94.9 4.1 1 ─────────────────────────────────────

[0074]

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In the above general formula V-2, x, y and z
Is shown below. ──────────────────────────────────── x yz (mol%) (mol%) (mol% ) ──────────────────────────────────── Polymer No. 10 86.3 1.7 12 Polymer No. 11 81.7 0.3 18 Polymer No. 11a 87.7 0.3 12 Polymer No. 12 83.0 5.0 12 Polymer No. 13 89.0 10.0 1 Polymer No. 13a 78.0 10.0 12 ─────────────────────────────────────

[0076]

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Examples of n, x, y and z in the above general formula V-3 are shown below. ──────────────────────────────────── n x yz (mol%) (mol%) (mol %) ──────────────────────────────────── Polymer No. 14 2 80.3 1.7 18 Polymer No. 15 3 87.5 0.5 12 Polymer No. 16 4 94.0 5.0 1 Polymer No. 16a 4 83.0 5.0 12 Polymer No. 17 5 86.9 1.1 12 Polymer No. 18 6 87.7 0.3 12 ─────────────────────────────────────

[0078]

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Examples of n, x, y and z in the above general formula V-4 are shown below. ──────────────────────────────────── n x yz (mol%) (mol%) (mol %) ──────────────────────────────────── Polymer No. 19 2 87.8 0.2 12 Polymer No. 20 2 87.5 0.5 12 Polymer No. 21 3 94.4 0.6 5 Polymer No. 21a 3 87.4 0.6 12 Polymer No. 22 4 86.4 1.6 12 Polymer No. 23 5 96.0 2.0 2 Polymer No. 23a 5 86.0 2.0 12 Polymer No. 24 6 84.8 3.2 12 ─────────────────────────────────────

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In the above general formula V-5, examples of n, x, y and z are shown below. ──────────────────────────────────── n x yz (mol%) (mol%) (mol %) ──────────────────────────────────── Polymer No. 25 2 87.5 0.5 12 Polymer No. 26 3 97.4 0.6 2 Polymer No. 26a 3 87.4 0.6 12 Polymer No. 27 4 86.4 1.6 12 Polymer No. 28 5 80.0 2.0 18 Polymer No. 29 6 84.8 3.2 12 ─────────────────────────────────────

[0082]

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Examples of Y, x, y and z in the above general formula V-6 are shown below. ──────────────────────────────────── Y x yz (mol%) (mol%) (mol%) %) ──────────────────────────────────── Polymer No. 30 No. 30-Y 86.3 1.7 12 Polymer No. 31 No. 31-Y 97.3 1.7 1 Polymer No. 32 No. 32-Y 87.4 0.6 12 Polymer No. 33 No. 33-Y 80.8 1.2 18 Polymer No. 34 No. 34-Y 86.3 1.7 12 ─────────────────────────────────────

[0084]

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[0085]

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In the above general formula V-7, x, y and z
Is shown below. ──────────────────────────────────── x yz (mol%) (mol%) (mol% ) ──────────────────────────────────── Polymer No. 35 87.8 0.2 12 Polymer No. 36 88.0 0.003 12 Polymer No. 37 87.86 0.14 12 Polymer No. 38 87.94 0.06 12 Polymer No. 39 87.2 0.8 12 Polymer No. 40 98.5 0.5 1 Polymer No. 41 97.8 0.2 2 Polymer No. 42 96.5 2.5 1 Polymer No. 43 94.9 4.1 1 Polymer No. E 86.9 1.1 12 Polymer No. F 98.5 0.5 1 ─────────────────────────────────────

[0087]

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In the general formula V-8, examples of n, x, y and z are shown below. ──────────────────────────────────── n x yz (mol%) (mol%) (mol %) ──────────────────────────────────── Polymer No. 44 3 87.8 0.2 12 Polymer No. 45 5 87.85 0.15 12 Polymer No. 46 6 87.7 0.3 12 Polymer No. 47 8 87.7 0.3 12 ─────────────────────────────────────

[0089]

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Examples of Y, x, y and z in the above general formula V-9 are shown below. ──────────────────────────────────── Y x yz (mol%) (mol%) (mol%) %) ──────────────────────────────────── Polymer No. 48 No. 48-Y 96.2 1.8 2 Polymer No. 49 No. 49-Y 84.2 0.8 15 Polymer No. 50 No. 50-Y 84.9 3.1 12 Polymer No. 51 No. 51-Y 87.5 2.5 10 ──────────────────────────────────────

[0091]

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[0092]

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In the above general formula V-10, n, x, y
Examples of z and z are shown below. ──────────────────────────────────── n R x y z (mol%) (mol%) ( Mol%) ──────────────────────────────────── Polymer No. 52 6 H 86.4 1.6 12 Polymer No. 53 4 H 87.2 0.8 12 Polymer No. 54 4 H 84.7 3.3 12 Polymer No. 55 5 CH ₃ 78.8 6.2 15 Polymer No. 56 9 CH ₃ 94.2 3.8 2 Polymer No. 57 3 H 85.0 5.0 10 ─────────────────────────────────────

[0094]

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In the above general formula V-11, n, x, y
Examples of z and z are shown below. ──────────────────────────────────── n R x y z (mol%) (mol%) ( Mol%) ──────────────────────────────────── Polymer No. 58 2 H 87.5 2.5 10 Polymer No. 59 4 H 84.5 0.5 15 Polymer No. 60 5 CH ₃ 97.8 0.2 2 Polymer No. 61 6 CH ₃ 94.5 4.1 1 Polymer No. 62 9 H 97.3 1.7 1 ──────────────────────────────────────

The above-mentioned specific polyvinyl alcohol is a compound having a part of the group of the specific unit (y or y1) of the general formula (I) or (III) or a group of the general formula (II) (eg,
It can be obtained by reacting a compound of the general formula (IIa)) with polyvinyl alcohol. Such groups are
It is capable of reacting with polyvinyl alcohol to form an ester bond, a urethane bond, an acetal bond, or the like. As the solvent (reaction solvent) for dissolving the polyvinyl alcohol and the compound having the specific group, various solvents from polar solvents to nonpolar solvents can be used. As an example, N, N-dimethylformamide (DM
F), dimethyl sulfoxide (DMSO), N, N-dimethylacetamide, polar solvents such as pyridine, tetrahydrofuran, ethers such as 1,2-dimethoxyethane, halogenated hydrocarbons such as dichloromethane and chloroform, and benzene and hexane. The non-polar solvent can be mentioned. These may be used alone or in combination. DMSO and ethers are particularly preferable.

A catalyst may be used in the reaction, if necessary. The base catalyst used in the case of esterification with a mixed acid anhydride and an acid halide may be either organic or inorganic. For example, hydroxide (eg, sodium hydroxide, potassium hydroxide, ammonium hydroxide),
Alkoxide (eg, sodium methoxide, sodium ethoxide, potassium-t-butoxide), metal hydride (eg, sodium hydride, calcium hydride), amine (eg, pyridine, triethylamine, piperidine, 1,
8-diazabicyclo [5,4,0] -7-undecene (DBU)), carbonates (eg sodium carbonate, potassium carbonate, sodium hydrogen carbonate), acetates (eg sodium acetate, potassium acetate). be able to. Amines are particularly preferable, and they may be used as a solvent.

As a catalyst used in the case of urethanization with an isocyanate, an alkoxide (eg, sodium methoxide, sodium ethoxide, potassium-t-
Butoxide), metal compounds (eg, dilauric acid di-n-)
Butyltin, tin octanoate, zinc acetylacetonate), amines (eg, pyridine, triethylamine, piperidine, 1,8-diazabicyclo [5,4,0] -7-)
Examples include undecene (DBU), tetramethylbutanediamine (TMBDA), and 1,4-diaza [2,2,2] bicyclooctane (DABCO).

Examples of the catalyst used in the case of acetalization with an aldehyde include mineral acids (eg sulfuric acid, hydrochloric acid), carboxylic acids (eg chloroacetic acid, trifluoroacetic acid, salicylic acid and its derivatives), sulfonic acids (eg methane). Examples thereof include sulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid), boron trifluoride, phosphorus pentoxide, and ion exchange resins (eg, Amberlyst).

The reaction temperature for reacting the compound having the above specific group with polyvinyl alcohol is -80 to 1
The range of 50 ° C is general, the range of -20 to 120 ° C is preferable, and the range of -5 to 90 ° C is particularly preferable. In the reaction, the ratio of the compound having the specific group to the repeating unit of polyvinyl alcohol (preparation ratio) is 1 in terms of molar ratio.
/ 100 to 1/1 (compound / repeating unit) is preferable, and 1/50 to 1/5 is particularly preferable. In order to obtain the target polymer from the reaction mixture, it is usually purified by a reprecipitation method by adding a poor solvent to the reaction mixture, dialysis, and lyophilization. These operations are appropriately repeated, and /
Alternatively, they can be performed in an appropriate combination.

The following is a synthesis example of the specific polyvinyl alcohol of the present invention. [Synthesis Example 1] (Synthesis of Polymer No. 1) 30 equipped with a stirrer
14.7 g of polyvinyl alcohol (trade name: MP Polymer MP-203; manufactured by Kuraray Co., Ltd .; saponification degree: 88 mol%) and molecular sieve 4 in a 0 ml three-necked flask.
100 ml of dimethyl sulfoxide previously dehydrated with A
Was added and dissolved at room temperature with stirring. The temperature was raised to 70 ° C and methacryloyloxyethyl isocyanate 0.77 was added.
A solution of 6 g of dimethyl sulfoxide in 15 ml was added dropwise. After stirring for 2 hours as it was, the mixture was filtered using a paper towel to remove impurities such as dust, and then dropped into 1.25 liters of ethyl acetate with stirring to precipitate a polymer. The precipitate (polymer) was collected by filtration, immersed in 600 ml of methanol, washed with stirring, filtered again, and dried to give 14.0 g of a lumpy polymer (No. 1) (yield 9
1%).

NMR spectrum (solvent DMSO-d ₆ ) Obtained polymer No. In addition to the main chain protons, hydroxyl group protons, acetyl group protons, the raw material MP-2
The following protons, which are not recognized in No. 03, were recognized with weak intensity. δ = 5.7, 6.1 ppm: belonging to vinyl group proton

(Measurement of visible absorption spectrum of polymer No. 1 and determination of introduction rate y of methacryloyl group) 50 ml
Polymer No. 0.015 g of 1 was accurately weighed and distilled water was added to prepare a 0.03% aqueous solution. The visible absorption spectrum of this solution was measured with a visible absorption ultraviolet-visible spectrophotometer (UV-2200, manufactured by Shimadzu Corporation). Maximum absorption wavelength (λmax) = 202nm Absorbance (202nm) = 0.839

On the other hand, polymer No. Polyvinyl alcohol (MP-203,
The absorption spectrum of Kuraray Co., Ltd. was measured. 202
The absorbance at nm was 0.504. Further, a urethane compound 1 × 10 ⁻⁴ M methanol solution obtained when the isocyanate compound having a methacryloyl group used in the above synthesis was reacted with methanol was prepared, and the absorption spectrum was measured in the same manner. Maximum absorption wavelength (λmax) = 202 nm Absorbance = 0.903 Molecular extinction coefficient (ε) = 8.42 × 10 ⁴ M ⁻¹ · cm Therefore, the polymer No. It is clear that the increase in the absorbance at λ max = 202 nm of 1 was due to the introduction of methacryloyloxyethyl isocyanate into the hydroxyl group of polyvinyl alcohol. The introduction rate (y) was determined from the measured value of the above absorbance (y = 1.7).

[Synthesis Examples 2, 3 and 4] (Synthesis of Polymers No. 2, No. 3 and No. 4) In the same manner as in Synthesis Example 1, polymer Nos. 2, 3 and 4 were synthesized. Polymer No. The visible absorption spectrum measurement results of 2, 3 and 4 are as follows, and the introduction rate y was determined from this. λmax Abs210 y Polymer No. 2 202nm 1.423 3.0 3 202nm 0.653 0.3 4 202nm 1.532 (0.001% aqueous solution) 18.0

[Synthesis Example 5] (Synthesis of Polymer No. 5) Polymer No. 5 was prepared in the same manner as in Synthesis Example 1 except that the reaction temperature was changed from 70 ° C. to room temperature. 5 was obtained. [Synthesis Examples 6 to 34] (Synthesis of Polymer Nos. 6 to 34) Basically, Synthesis Example 1
In the same manner as in Polymer No. 6-34 were obtained.

[Synthesis Example 35] (Synthesis of Polymer No. 35) 500 equipped with a stirrer
Polyvinyl alcohol (MP-20
2) (3, manufactured by Kuraray Co., Ltd.) and 225 ml of dimethyl sulfoxide (DMSO) previously dehydrated using molecular sieve 4A were added and dissolved at room temperature with stirring to prepare a polyvinyl alcohol / DMSO solution. On the other hand, in another 50 ml three-necked flask equipped with a stirrer, 1.55 ml (20 mmol) of methanesulfonyl chloride
And 20 ml of tetrahydrofuran (THF) are added, and 5.28 g (20 mmol) of compound 2-2 (the above compound number; 4- (4-acryloyloxybutoxy) benzoic acid) and 3.42 ml (20 mmol) of diisopropylethylamine are added to T.
The solution dissolved in 20 ml of HF was added dropwise with stirring under ice cooling. After dropwise addition, stirring was continued for 30 minutes under ice cooling to prepare a mixed acid anhydride of compound 2-2 and methanesulfonic acid.

To the above polyvinyl alcohol / DMSO solution, 3.42 ml (20 mm) of diisopropylethylamine was added.
ol) and 0.24 g (2 mmol) of dimethylaminopyridine were added, and the above mixed acid anhydride was slowly added with stirring at room temperature. The mixture was stirred at room temperature for 6 hours and then left overnight. The reaction solution was slightly yellow. After filtering with a paper towel to remove impurities such as dust,
Add dropwise to 2.25 liters of ethyl acetate with stirring,
The polymer was precipitated. The precipitate (polymer) had a white fluffy appearance. The precipitate was collected by filtration and dried to obtain 22.1 g (yield 84%) of a lumpy polymer (No. 35).

NMR spectrum (solvent DMSO-d ₆ ) Polymer No. In 35, in addition to the main chain proton, the hydroxyl group proton, and the acetyl group proton, the following protons not found in the raw material MP-203 were found with weak intensity. δ = 7.9, 7.0 ppm: attributed to phenylene group proton δ = 6.3, 6.2, 5.9 ppm: attributed to vinyl group proton (UV absorption spectrum measurement of polymer No. 35 and determination of introduction rate y) ) Polymer N in a 100 ml volumetric flask
o. Accurately weigh 0.1 g of 35, add distilled water,
A 0.1% aqueous solution was prepared. Using this solution, its absorption spectrum was measured by an ultraviolet-visible spectrophotometer (UV-2200,
It was measured using Shimadzu Corporation. Maximum absorption wavelength (λmax) = 260 nm Absorbance (Abs260) = 0.788

On the other hand, polymer No. Polyvinyl alcohol (MP-203,
The absorption spectrum of Kuraray Co., Ltd. was measured. 220
In the wavelength range of up to 400 nm, no absorption maximum was observed, and weak absorption was observed, with a tail extending from the short wavelength side to the long wavelength side. 26
The absorbance at 0 nm was 0.011. Furthermore, compound 2-
A methyl ester 1 × 10 ⁻⁴ M methanol solution of 2 was prepared, and the absorption spectrum was measured in the same manner. Maximum absorption wavelength (λmax) = 260 nm Absorbance (Abs260) = 1.84 Molecular extinction coefficient (ε) = 1.84 × 10 ⁴ M ^-1 · cm. Therefore, the polymer No. 35 λ max = 26
In the 0 nm absorption band, it is clear that the compound 2-2 was introduced into the hydroxyl group of polyvinyl alcohol by an ester bond. The introduction rate (y) was determined from the measured value of the above absorbance (y = 0.21).

[Synthesis Examples 36, 37 and 38] (Synthesis of Polymer Nos. 36, 37 and 38) Synthesis Example 35
In the same manner as in Polymer No. 36, 37 and 38 were synthesized. However, the amounts of reagents used are as shown in the table below. The yield and yield are also shown in the table below.

──────────────────────────────────── Polymer No. 36 No. 37 No. 38 ──────────────────────────────────── [Esterification of PVA] PVA MP-203 (g) 26.4 26.4 26.4 DMSO (ml) 225 225 225 Diisopropylethylamine (ml) 0.34 1.71 10.3 Dimethylaminopyridine (g) 0.024 0.12 0.72 ───────────────────────── ───────────── [Preparation of mixed acid anhydride] Methanesulfonyl chloride (g) 0.16 0.78 4.65 Tetrahydrofuran (ml) 2 10 60 Compound 2-2 (g) 0.53 2.64 15.84 Diisopropylethylamine ( ml) 0.34 1.71 10.3 Tetrahydrofuran (ml) 2 10 60 ──────────────────────────────────── Yield (G /%) 21.1 / 80 23.5 / 89 22.3 / 84 ─────────────────────── ─────────────

Polymer No. The ultraviolet absorption spectrum measurement results of 36, 37 and 38 are as follows. From this, the introduction rate y was determined. λmax Abs260 y Polymer No. 36 260nm 0.023 0.003 37 260nm 0.553 0.14 38 260nm 0.132 0.06

[Synthesis Example E] (Synthesis of Polymer No. E) Polymer No. E was prepared in the same manner as in Synthesis Example 38 except that the reaction conditions in Synthesis Example 38 were changed from room temperature of 6 hours to 45 ° C. of 8 hours. E was obtained.

[Synthesis Example 39] (Synthesis of Polymer No. 39) 500 equipped with a stirrer
Add a polyvinyl alcohol (MP-
203, manufactured by Kuraray Co., Ltd.) 26.4 g and DMSO 168 ml previously dehydrated using molecular sieve 4A
Was added and dissolved at room temperature with stirring to prepare a DMSO solution of polyvinyl alcohol. On the other hand, in another 200 ml three-necked flask equipped with a stirrer, 3.24 ml (42 mmol) of methanesulfonyl chloride and 21 m of THF were placed.
1 was added, and the compound 2-211.1 g (42 mmol) and diisopropylethylamine 7.32 ml (42 mmo
A solution prepared by dissolving l) in 42 ml of THF was added dropwise while stirring under ice cooling. Continue stirring under ice cooling for 30 minutes after dropping,
A mixed acid anhydride of compound 2-2 and methanesulfonic acid was prepared.

Diisopropylethylamine (7.32 ml, 42 m) was added to the DMSO solution of polyvinyl alcohol.
mol) and 4-N, N-dimethylaminopyridine 0.5
1 g (4.2 mmol) was added, and the above mixed acid anhydride was added dropwise uniformly over 1 hour with stirring while heating to 45 ° C. After the dropping was completed, the mixture was stirred at 45 ° C. for another 3 hours,
It was cooled to room temperature and filtered using a paper towel. 134 ml of 2-propanol was added to this reaction liquid to give 1.68.
The polymer was precipitated by dropwise addition into 1 l of ethyl acetate with stirring. The precipitate (polymer) is filtered off and then 700
The mixture was poured into ml of methanol, washed with stirring, and then filtered again. It was dried under reduced pressure at room temperature to obtain 24.0 g (yield 91%) of a slightly yellow small block polymer (No. 39). The polymer No. The ultraviolet absorption spectrum was measured in the same manner as in No. 35, and the introduction rate y was determined from the absorbance at 260 nm (y = 0.80).

[Synthesis Examples 40, 41, 42 and 43] (Synthesis of Polymer Nos. 44, 45, 46 and 47) In Synthesis Example 35, instead of Compound 2-2, Compound 2 was used.
1, Compound 2-3, Compound 2-4, and Compound 2-6 were used for synthesis in the same manner as in Synthesis Example 35 to obtain polymer N.
o. 44, 45, 46 and 47 were obtained.

[Synthesis Examples 44 and 45] (Synthesis of Polymer Nos. 53 and 54) In a 500 ml three-necked flask equipped with a stirrer, 44 g of polyvinyl alcohol (MP-203, manufactured by Kuraray Co., Ltd.) and p-toluenesulfonic acid. DMSO2 previously dehydrated with 4.4 g (23 mmol) of monohydrate and Molecular Sieve 4A
00 ml was added and dissolved at room temperature with stirring. 4- (4-acryloyloxybutyloxy) benzaldehyde (2.0 g of polymer No. 53,
Polymer No. 54g 8.0g) and DMSO 80
A solution consisting of ml was added and stirring was continued at room temperature for 5 hours.
The polymer was precipitated by dropping the reaction mixture into 3 liters of ethyl acetate with stirring. The precipitate (polymer) was collected by filtration, then poured into 1 l of methanol, washed with stirring, and then collected again by filtration. It was dried under reduced pressure at room temperature to obtain a white small block polymer. Polymer No. 53 Yield 41 g (Yield 89%) Polymer No. 54 Yield 43 g (83% yield)

NMR spectrum (solvent DMSO-d ₆ ) Polymer No. In addition to the main chain protons, hydroxyl group protons, and acetyl group protons, 53 and 54 contain the raw material MP.
The following protons, which are not found in -203, were found with weak intensity. δ = 7.3, 6.9 ppm: attributed to phenylene group protons δ = 6.3, 6.2, 5.9 ppm: attributed to vinyl group protons δ = 5.5 ppm: attributed to acetal protons Aldehyde exists In some cases, δ = 10
No signal could be observed near ppm. Therefore, it is clear that the obtained polymer was acetalized as intended.

Further, an acetal of 4- (4-acryloyloxybutyloxy) benzaldehyde and trimethylenediol was prepared, and then 1 × 1 of this acetal was prepared.
A 0 ⁻⁴ M methanol solution was prepared and its absorption spectrum was measured. Maximum absorption wavelength (λmax) = 272 nm Absorbance (Abs272) = 1.66 Molecular extinction coefficient (ε) = 1.66 × 10 ⁴ M ⁻¹ · cm Polymer No. For polymer Nos. 53 and 54, the polymer Nos. The ultraviolet absorption spectrum was measured in the same manner as in No. 35, and the introduction rate y was determined from the absorbance at 272 nm. It was 0.8 and 3.3, respectively.

The alignment film of the present invention may be composed of the specific polyvinyl alcohol of the present invention alone or a mixture with a conventionally known polymer for an alignment film. In the case of mixtures, generally known polymers can be used up to 90% by weight of the total polymer,
Particularly, it is preferably used at 70% by weight or less.

Other than the above-mentioned specific polyvinyl alcohol of the present invention, examples of the polymer having a polymerizable group that can be used in the alignment film of the present invention include a polyimide having vinyl, oxiranyl or aziridinyl, and vinyl, oxiranyl or aziridinyl. Gelatin having These polymers can be synthesized by using a polymer having a hydroxyl group or an amino group introduced, in the same manner as in the synthesis of the above-mentioned specific polyvinyl alcohol. For example, the introduction of the polymerizable group to the polyimide, by reacting a polyhydric alcohol to the carboxyl group of the polyamic acid, to introduce a hydroxyl group to the polyamic acid, having a polymerizable group used in the synthesis of the specific polyvinyl alcohol It can be carried out by reacting a compound (eg, the compound of the general formula (IIa) or its isocyanate compound) with the hydroxyl group of the polyamic acid, and then polymerizing the polyamic acid having the polymerizable group. The introduction of the polymerizable group into gelatin can be carried out by reacting the ε-amino group of the lysine residue of gelatin with the compound having the polymerizable group used in the synthesis of the above specific polyvinyl alcohol.

Examples of other known polymers that can be used in the alignment film of the present invention include polymethylmethacrylate, acrylic acid / methacrylic acid copolymer, styrene / maleinimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol. , Poly (N-methylol acrylamide), styrene / vinyl toluene copolymer, chlorosulfonated polyethylene, nitrocellulose, polyvinyl chloride, chlorinated polyolefin, polyester, polyimide, vinyl acetate / vinyl chloride copolymer, ethylene / vinyl acetate Mention may be made of copolymers, carboxymethylcellulose, polyethylene, polypropylene and polycarbonate.

The alignment film of the present invention is formed by coating a coating solution containing the above-mentioned specific polyvinyl alcohol, which is a material for forming an alignment film, on a transparent support, followed by heating and drying to form a polymer layer. Can be formed by performing an alignment treatment such as a rubbing treatment. Examples of the coating method include a spin coating method, a dip coating method, an extrusion coating method and a bar coating method. In particular, the E-type coating method is preferable. The film thickness is preferably 0.1 to 10 μm. The heat drying can be performed at 20 ° C to 110 ° C, particularly preferably 60 ° C to 100 ° C, particularly preferably 80 ° C to 100 ° C. The drying time can be 1 minute to 36 hours. It is preferably 5 minutes to 30 minutes.

The alignment film is formed of the polymer layer, L as described above.
It can be obtained by performing an alignment treatment such as a rubbing treatment by utilizing a treatment method which is widely adopted as a liquid crystal alignment treatment step of CD. The alignment film functions to define the alignment direction of a liquid crystal compound such as a liquid crystal discotic compound provided thereon. The rubbing treatment is generally performed by rubbing the surface of the polymer layer in a certain direction using paper, gauze, felt, rubber or velvet, fibers such as polyamide and polyester, and the like. It is preferably carried out by rubbing the surface of the polymer layer with a rubbing roll around which a rubbing cloth such as velvet is wound. The rubbing may be performed by a batch method or a continuous method.

The optical compensation sheet of the present invention can be obtained by forming a layer of liquid crystalline compound (optically anisotropic layer) on the alignment film. The liquid crystalline compound may be a rod-shaped liquid crystalline compound or a discotic liquid crystalline compound. Discotic liquid crystalline compounds are preferred. The liquid crystalline compound preferably has a polymerizable group in order to chemically bond with the polymer of the alignment film. These liquid crystal compounds are described in, for example, Quarterly Chemistry Review, No. 22, Liquid Crystal Chemistry (199
4 years). Examples of rod-shaped liquid crystal compounds include biphenyl derivatives, benzoic acid phenyl ester derivatives, benzylideneaniline derivatives, azobenzene derivatives, azoxybenzene derivatives, stilbene derivatives, and those in which the benzene ring is saturated or replaced with a heterocycle. Can be mentioned. Examples of these are C _a H _{2a + 1} -Ph-Ph-CN, C _a H _{2a + 1} -Cy-Ph-CN, C _a
H _{2a + 1} -Ph-COO-Ph-CN, C _a H _{2a + 1} -Ph-COO-Ph (F) -CN, C _a H
_{2a + 1} -Cy-COO-Ph-O (C _b H _{2b + 1} ), C _a H _{2a + 1} -Cy-Ph-O (C
_b H _{2b + 1} ), C _a H _{2a + 1} -Cy-Ph-Ph-O (C _b H _{2b + 1} ), or C _a H
_{2a + 1} -Cy-C ₂ H ₄ -Ph-Ph (F) -C _b H _{2b + 1} (wherein Ph is phenylene, Cy is cyclohexene, Ph (F) is F-substituted phenylene,
a and b each represent an integer of 1 to 24. A compound having a polymerizable group (eg, acryloyloxy, methacryloyloxy, vinyl, vinyloxy, styryl or chloroacryloxy) introduced into the compound represented by D. J. Broer et al., Makromol. C
hem. , 189, 185 (published in 1988) and 190, 2255 (1989).
The compounds described in can be mentioned.

The above-mentioned discotic liquid crystal compound generally has a discotic structure as the mother nucleus of the molecular center, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group or the like as its linear chain. It has a radially substituted structure, exhibits liquid crystallinity, and includes what is generally called discotic liquid crystal. The disk-shaped morphological characteristics of the mother nucleus portion excluding the side chain portion can be expressed as follows, for example, with respect to the hydrogen-substituted compound as its original compound. First, the size of the molecule of the mother nucleus is determined as follows. 1) Design a molecule (mother nucleus molecule) as close to a plane as possible, preferably a planar molecular structure. In this case, it is preferable to use the standard values according to the mixture of the orbits as the bond distance and the bond angle. Can be referenced. 2) Using the structure obtained in 1) as an initial value, the structure is optimized by the molecular orbital method or the molecular force field method. Examples of the method include Gaussian92, MOPAC93,
CHARMm / QUANTA and MM3 are mentioned, and Gaussian92 is preferable. 3) Give each structure-optimized atom a sphere defined by the van der Waals radius, and describe the shape of the molecule. 4) Let a, b, and c be the three edges of the rectangular parallelepiped that can accommodate the molecular portion having the shape obtained in 3). In order to reduce the arbitrariness further, it is preferable to perform the above 3) and the following as follows. 3 ′) The center of gravity of the structure obtained by the structure optimization is moved to the origin, and the coordinate axes are set to the principal axes of inertia (inertia tensor ellipse). The main axis of the body). 4 ') Give each atom a sphere defined by the van der Waals radius, and describe the shape of the molecule. 5 ') The lengths in the respective coordinate axis directions are measured on the van der Waals surface, and these are designated as a, b, and c, respectively. The morphology of the nucleus of the discotic compound using a, b, and c obtained by the above procedure is a ≧ b> c and a ≧ b ≧ a /
It can be defined as a structure that satisfies 2. Preferably, the structure satisfies a ≧ b> c and a ≧ b ≧ 0.7a. Further, it is more preferable that b / 2> c.

Examples of the discotic liquid crystalline compound which can be used in the present invention include: Chemical Society of Japan, Quarterly Chemistry Review, N.
o. 22. Benzene derivative, triphenylene derivative, truxene derivative, phthalocyanine derivative, porphyrin derivative, anthracene derivative, azacrown derivative, cyclohexane derivative, β-diketone metal complex derivative, and phenyl described in Chemistry of Liquid Crystals (published in 1994). It is an acetylene macrocycle, and
The cyclic compounds and their heteroatomic electronic structures such as those described in "Chemical Review No. 15 New Aromatic Chemistry" edited by The Chemical Society of Japan (1977, published by The University of Tokyo Press) can be mentioned. Further, as in the case of the above metal complex,
A disc-shaped molecule may be formed by forming an aggregate of a plurality of molecules by hydrogen bond, coordination bond, or the like.

The discotic liquid crystal compound has a discotic structure as a mother nucleus at the center of the molecule, and a linear alkyl group, an alkoxy group, a substituted benzoyloxy group or the like is radially substituted as its side chain. Have a structure. Preferably the mother nucleus compound is to form a discotic nematic (N _D) phase, particular preference may be mentioned triphenylene and truxene. Examples of the side chain include an alkyl group, an alkoxy group, an alkylthio group, an acyloxy group, an alkoxycarbonyl group, and a halogen, and an alkyl group, an alkoxy group, an alkylthio group, and an acyloxy group are particularly preferable. These groups are C.I. Hansch, A .; L
eo, R.E. W. Taft, Chemical Review Magazine (Ch
em. Rev .. ) 1991, 91, 165-195
Page (American Chemical Society). Further, in the side chain, for example, ether group, ester group, carbonyl group,
A functional group such as a thioether group, a sulfoxide group, a sulfonyl group, an amide group, or an aryl group or a heterocyclic group may be contained in the side chain.

The discotic liquid crystalline compound of the present invention can form a new bond in itself as a substituent or can bond with another compound (same or different), and the alignment film can be formed. It is preferable to have a group capable of chemically bonding to the polymer of. Such groups react with the same group to form a new bond, or react with a different group to form a new bond. Examples of such groups are S. R. Sandler and W.D. Karlow (SR Sandler, W. Karo)
By Organic Functional Group Preparat
ions) Volumes 1 and 2 (Academic Press, New York, London, 1968). Of these, a polymerizable group is preferable, and for example, a multiple bond (the constituent atom may be either a carbon atom or a non-carbon atom), a heterocyclic ring such as oxirane, or aziridine is preferable. A. M. Research report by Hikmet et al. [Macr
omolecules, 25, 4194 (1992)] and [Polymer, 34, No. 8, 1763 (1993).
Year)], D. J. Broer et al.'S research report [Macromolecule
s., 26, 1244 (1993)], double bonds, that is, acrylic groups, vinyl ether groups and epoxy groups are preferred.

Examples of preferable discotic liquid crystal compounds include the following.

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In D-1-1 above, R ⁶¹ , R ⁶² ,
Examples of R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and J are shown below. ──────────────────────────────────── Compound R ⁶¹ R ⁶² R ⁶⁴ R ⁶⁵ R ⁶⁶ J ── ────────────────────────────────── TP-1 HHHHH-(CH ₂ ) ₂ OCO- TP-2 HHHHH _{- (CH 2) 3 OCO- TP} -3 HHHHH - (CH 2) 4 OCO- TP-4 HHHHH - (CH 2) 5 OCO- TP-5 HHHHH - (CH 2) 6 OCO- TP-6 HHHHH - ( CH ₂ ) ₇ OCO- TP-7 HHHHH-(CH ₂ ) ₈ OCO- TP-8 HHHH CH _3- (CH ₂ ) ₉ OCO- TP-9 HHHHC ₂ H _5- (CH ₂ ) ₆ OCO- TP-10 _{CH 3 HHHC 2 H 5 - (} CH 2) 6 OCO- TP-11 CH 3 CH 3 HHH - (CH 2) 2 OCO- TP-12 H CH 3 HHH - (CH 2) 3 OCO- TP-13 CH 3 HHHH-(CH ₂ ) ₄ OCO- TP-14 CH ₃ HHHH-(CH ₂ ) ₅ OCO- TP-15 CH ₃ HHHH-(CH ₂ ) ₆ OCO- TP-16 CH ₃ CH ₃ HHH-(CH ₂ ) ₇ OCO- TP-17 H CH ₃ HHH-(CH ₂ ) ₈ OCO- TP-18 CH ₃ HHH CH _3- (CH ₂ ) ₉ OCO- TP-19 CH ₃ HHHC ₂ H _5- (CH ₂ ) ₆ OCO - _{P-20 H CH 3 HH CH} 3 - (CH 2) 6 OCO- TP-21 HHHH nC 3 H 7 - (CH 2) 2 OCO- TP-22 HHHHH - (CH 2) 3 OC 2 H 4 OCO- TP −23 HHHHH-(C ₂ H ₄ O) ₂ C ₃ H ₆ OCO- TP−24 CH ₃ HHHH-(C ₂ H ₄ O) ₂ CO- TP−25 HHHHH-(C ₂ H ₄ O) ₃ CO- TP-26 HHH CH ₃ CH _3- (CH ₂ ) ₄ CO- TP-27 HH CH ₃ HH-(CH ₂ ) ₅ OCO- TP-28 HH CH ₃ HH-(CH ₂ ) ₆ OCO- TP-29 HH CH ₃ HH-(CH ₂ ) ₇ OCO- TP-30 HH CH ₃ HH-(CH ₂ ) ₈ OCO- ──────────────────────── ────────────

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Further, these discotic liquid crystalline compounds can be used not only alone but also as a mixed composition. Compounds that can be added to the discotic liquid crystalline compound include:
Discotic liquid crystalline compound having no liquid crystal properties, or other compounds (low molecular weight, high molecular weight, liquid crystalline, non-liquid crystalline, which can form new bonds between molecules or within molecules, Which may not be obtained; eg, plasticizers, polymerizable monomers, surfactants, polymers).

As described above, the optical compensatory sheet of the present invention is generally subjected to a rubbing treatment of a layer of a polymer having a functional group such as a polymerizable group (eg, a specific polyvinyl alcohol of the present invention) on a transparent support. Forming an alignment film that is a film,
Then, it can be obtained by forming an optically anisotropic layer on the alignment film. The optically anisotropic layer of the present invention is formed of a liquid crystal compound, preferably a discotic liquid crystal compound. As described above, these compounds preferably have a functional group such as vinyl, oxiranyl or aziridinyl. The above-mentioned optically anisotropic layer is generally formed by applying a solution of a liquid crystal compound (and other compounds) such as a discotic liquid crystal compound in a solvent onto the alignment film, drying the solution, and then applying a discotic nematic phase forming temperature (disc It is obtained by heating to a tick liquid crystal compound) and then cooling while maintaining the alignment state (discotic nematic phase). Alternatively, the optically anisotropic layer, a discotic liquid crystal compound having a polymerizable group (and other compounds (eg, polymerizable monomer, photopolymerization initiator)) is applied to the alignment film a solution prepared by dissolving it in a solvent, It is dried and then heated to the discotic nematic phase formation temperature and then polymerized (U
(For example, irradiation with V light) and further cooling. The discotic liquid crystal compound having a polymerizable group loses its liquid crystallinity after being polymerized and cured as described above. The discotic nematic liquid crystal phase-solid phase transition temperature of the discotic liquid crystal compound used in the present invention is preferably 70 to 300 ° C, particularly 70 to 170 ° C.
Is preferred. The thickness of the optically anisotropic layer is 0.1 μm to 20
It is preferably μm, and can be applied in the same manner as the above-mentioned polyvinyl alcohol.

In the present invention, the alignment film is made of a polymer having a functional group such as vinyl, oxiranyl or aziridinyl. Therefore, when an optically anisotropic layer having the above functional group is formed on the alignment film and these two layers are irradiated with, for example, UV light, the functional groups (eg vinyl) of the alignment film and the optically anisotropic layer are By reacting with each other, these two layers will chemically bond. Even when the thus-obtained optical compensation sheet is stored or used for a long period of time, the optically anisotropic layer hardly peels from the alignment film. Therefore, the functional groups of the alignment film and the optically anisotropic layer are preferably those which react with each other, and particularly preferably a polymerizable group such as vinyl, oxiranyl or aziridinyl (particularly the same polymerizable group).

The optically anisotropic layer of the present invention generally has a minimum absolute retardation value other than 0 (having no optical axis) in a direction tilted from the normal direction of the optical compensation sheet.
FIG. 3 shows a typical configuration example of the optical compensation sheet including the optically anisotropic layer of the present invention. In FIG. 3, a transparent support 31, an alignment film 32, and a discotic compound layer (optically anisotropic layer) 33 are sequentially laminated to form an optical compensation sheet. R indicates the rubbing direction of the alignment film. n ₁ n ₂ and n ₃ represent the triaxial refractive index of the optical compensation sheet,
When viewed from the front, the relationship of n ₁ ≤n ₃ ≤n ₂ is satisfied. β is the inclination from the normal line 34 of the optically anisotropic layer in the direction showing the minimum value of Re (retardation). The negative uniaxiality that the optical compensation sheet of the present invention usually has is generally n ₁
<N ₂ = n ₃ is satisfied. Actually, | n ₂ −n ₃ | /
It suffices to satisfy | n ₂ −n ₁ | ≦ 0.2. TN-LC
In order to improve the viewing angle characteristics of D and TFT-LCD,
The direction showing the minimum absolute value of Re is preferably inclined by 5 to 50 degrees (mean value of inclination) from the normal line 34 of the optically anisotropic layer, and more preferably 10 to 40 degrees (the above β). Furthermore, the above-mentioned sheet has the following conditions: 50 ≦ [(n ₃ + n ₂ ) / 2−n ₁ ] × D ≦ 400 (n
m) (where D is the thickness of the sheet), and further, the following condition: 100 ≦ [(n ₃ + n ₂ ) / 2−n ₁ ] × D ≦ 400
(Nm)

FIG. 4 shows a typical constitution example of a liquid crystal display device provided with the optical compensation sheet of the present invention. In FIG. 4, a liquid crystal cell TNC including a pair of substrates provided with transparent electrodes and a twist-aligned nematic liquid crystal enclosed between the substrates,
A pair of polarizing plates A and B provided on both sides of the liquid crystal cell, and an optical compensation sheet RF arranged between the liquid crystal cell and the polarizing plate.
₁ , RF ₂ and the backlight BL are combined to form a liquid crystal display device. Only one optical compensation sheet may be provided (ie, RF ₁ or RF ₂ ). R ₁ indicates the rubbing direction of the optical compensation sheet RF ₁ when viewed from the front, and R ₂ indicates the rubbing direction of the optical compensation sheet RF ₂ . The solid arrow of the liquid crystal cell TNC represents the rubbing direction of the substrate on the polarizing plate B side of the liquid crystal cell TNC.
The dotted arrow NC indicates the rubbing direction of the substrate on the polarizing plate A side of the liquid crystal cell. PA and PB represent the polarization axes of the polarizing plates A and B, respectively.

[0150]

EXAMPLES The present invention will be described in more detail based on examples. [Examples 1 to 4 and Comparative Example 1] (Formation of Alignment Film) On a glass substrate, the following coating liquid containing polyvinyl alcohol shown in Table 1 described later was applied with a bar coater and dried by heating at 80 ° C for 10 minutes. To form a polymer layer having a thickness of 0.8 μm. (Hereinafter, "part" means "part by weight") [Coating liquid] Polyvinyl alcohol shown in Table 1 1.0 part Water 18.0 parts Methanol 6.0 parts The surface of the obtained polymer layer is rubbed. Roll outer diameter: 8
A rubbing treatment was carried out under the conditions of 0 mm, glass substrate transport speed: 100 m / min, rubbing roll rotation speed: 1000 rpm, and substrate transport tension: 1 kgf / cm substrate width to form an alignment film.

(Layer of discotic liquid crystalline compound (optically anisotropic layer)
Formation), a 10 wt% solution of TP-3 (the above triphenylene compound) in methyl ethyl ketone was spin coated on the alignment film of the glass substrate that had been rubbed.
A discotic liquid crystal compound layer (optically anisotropic layer) was formed by coating at 000 rpm and drying.

(Evaluation of orientation of discotic liquid crystal compound layer)
Using a polarizing microscope (OPTIPHOT-POL, manufactured by Nihon Kogyo Co., Ltd.), the glass plate provided with the alignment film and the optically anisotropic layer is heated on a hot stage (FP82 type, manufactured by METTLER), and its optical properties are measured. The orientation state of the anisotropic layer was observed. Example 1
.About.4 and the optically anisotropic layers obtained in Comparative Example 1 looked bright even under crossed Nicols and showed optical anisotropy. Table 1 shows the observation results of the obtained optically anisotropic layer.

[0153]

[Table 1] Table 1 ──────────────────────────────────── Example Polymer layer Orientation The polymer No. ──────────────────────────────────── Example 1 No. 1 uniform orientation Example 2 No. 35 Uniform orientation Example 3 No. 39 Uniform orientation Example 4 No. 53 Uniform Orientation ──────────────────────────────────── Comparative Example 1 MP-203 Schlieren Microstructure Remaining (( Kuraray Co., Ltd.) ────────────────────────────────────

[Examples 5 to 34 and Comparative Examples 2 to 3] (Preparation of Alignment Film) Triacetyl cellulose film (thickness 100 μm, manufactured by Fuji Photo Film Co., Ltd., Fujitac) is shown in Table 2 to be described later. The following coating solution containing alcohol was applied with a bar coater and heated and dried at 80 ° C. for 10 minutes to form a polymer layer having a film thickness of 0.8 μm. [Coating Liquid] Polyvinyl alcohol shown in Table 2 1.0 part Water 18.0 parts Methanol 6.0 parts The surface of the obtained polymer layer was rubbed roll outer diameter: 8
0 mm, film transport speed: 100 m / min, rubbing roll rotation speed: 1000 rpm, and film transport tension: 1 kgf / cm
A rubbing process was performed under the conditions of substrate width to form an alignment film.

(Layer of discotic liquid crystalline compound (optically anisotropic layer)
Formation of) A coating liquid for forming a discotic liquid crystalline compound layer having the following composition is coated on a rubbed alignment film on a film by a bar coater, and dried to obtain a discotic liquid crystalline compound. A coating layer was formed. [Coating liquid] Cellulose acetate butyrate 12 parts (CAB531, Eastman Chemical Co., Ltd.) Discotic liquid crystal compound TP-3 (the compound) 100 parts Tripropylene glycol diacrylate 10 parts (SR306, manufactured by Somar Corporation) Light Polymerization initiator 2 parts (Irgacure 907, manufactured by Ciba-Geigy Co., Ltd.) Methyl ethyl ketone 400 parts The film having this coating layer is passed through a heating zone of 140 ° C. for 2 minutes, and then the coating layer is irradiated with UV light to be cured. By doing so, a thin film (optically anisotropic layer, layer thickness 2 μm) in which the aligned state of the aligned discotic liquid crystal compound was fixed was formed, and an optical compensation sheet was obtained.

(Evaluation of Orientation of Disc-shaped Liquid Crystal Compound Layer (Optical Anisotropic Layer) Before and After Moisture and Heat Resistance Test) A film provided with an alignment film and an optical anisotropic layer was subjected to a hot stage (FP82).
Polarizing microscope (OPTI) while heating on a mold, METTLER
Using PHOT-POL, manufactured by Nippon Kogaku Co., Ltd., the orientation state of the optically anisotropic layer was observed. Examples 5 to 34 and Comparative Example 2
The optically anisotropic layers obtained in any of 3 to 3 looked bright even under crossed nicols and exhibited optical anisotropy. Table 2 shows the observation results of the obtained optically anisotropic layer. Furthermore, the orientation of the obtained film is 100 at 75 ° C. and a humidity of 95%.
After standing for a period of time, it was observed in the same manner as above, and the moist heat resistance was evaluated. Table 2 shows the obtained results. The orientation evaluation is
The procedure was as follows. AA: uniform orientation BB: schlieren structure remaining The moist heat resistance was evaluated as follows. AA: Uniform orientation BB: Occurrence of reticulation after 20 hours of heat and humidity resistance test CC: Occurrence of reticulation after 5 hours of heat and humidity resistance test

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[Table 2] Table 2 ──────────────────────────────────── Example Polymer layer Orientation The polymer No. Before moist heat resistance After moist heat resistance ───────────────────────────────────── Example 5 No. 1 AA AA Example 6 No. 2 AA AA Example 7 No. 3 AA AA Example 8 No. 4 AA AA Example 9 No. 5 AA AA Example 10 No. 5 / ^* MP-203 = 3/1 AA AA Example 11 No. 5 / ^** PVA-117 = 4/1 AA AA Example 12 No. 10 AA AA Example 13 No. 14 AA AA Example 14 No. 20 AA AA Example 15 No. 25 AA AA Example 16 No. 26 AA AA Example 17 No. 29 AA AA Example 18 No. 35 AA AA Example 19 No. 36 AA AA Example 20 No. 37 AA AA Example 21 No. 38 AA AA Example 22 No. 39 AA AA Example 23 No. 39 / ^* MP-203 = 3/1 AA AA Example 24 No. 39 / ^** PVA-117 = 4/1 AA AA Example 25 No. 44 AA AA Example 26 No. 45 AA AA Example 27 No. 48 AA BB Example 28 No. 49 AA AA Example 29 No. 51 AA AA Example 30 No. 53 AA AA Example 31 No. 35 / ^* MP-203 = 1/1 AA --- Example 32 No. EAA--Example 33 No. E / ^* MP-203 = 1/3 AA --- Example 34 No. E / ^** PVA-117 = 4/1 AA −− ───────────────────────────────────── Comparative Example 2 ^* MP-203 AA CC Comparative Example 3 ^** PVA-117 AA CC ─────────────────────────────── ───── Note: *, ** Made by Kuraray Co., Ltd.

[Examples 35 to 46 and Comparative Examples 4 to 9] In Example 5, the discotic liquid crystalline compounds shown in Table 3 were used in place of TP-3, and the polymer No. An optical compensation sheet was prepared in the same manner as in Example 5 except that the polymer shown in Table 3 was used instead of 1. With respect to the sheets obtained in Examples 35 to 46 and Comparative Examples 4 to 9, the orientations before and after the moisture and heat resistance test were evaluated in the same manner as in Example 5. Further, the obtained optically anisotropic layer exhibited high transparency under crossed Nicols, and optical anisotropy was observed. The results are shown in Table 3.

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[Table 3] Table 3 ──────────────────────────────────── Example Polymer layer Discotic Orientation Polymer No. Compound No. Compound No. Before moist heat resistance After moist heat resistance ──────────────────────────────────── Example 35 No. 1 TP-4 AA AA Example 36 No. 1 TP-5 AA AA Example 37 No. 1 TP-8 AA AA Example 38 No. 1 TP-17 AA AA Example 39 No. 1 TP-23 AA AA Example 40 No. 1 TP-28 AA AA Example 41 No. 39 TP-4 AA AA Example 42 No. 39 TP-5 AA AA Example 43 No. 39 TP-8 AA AA Example 44 No. 39 TP-17 AA AA Example 45 No. 39 TP-23 AA AA Example 46 No. 39 TP-28 AA AA ──────────────────────────────────── Comparative Example 4 Polyimide TP-4 BB CC Comparative Example 5 Polyimide TP-5 BB CC Comparative Example 6 Polyimide TP-8 BB CC Comparative Example 7 ^* MP-203 TP-17 AA CC Comparative Example 8 ^* MP-203 TP-23 AA CC Comparative Example 9 ^* MP-203 TP-28 AA CC ──────────────────────────────────── Note: * Made by Kuraray Co., Ltd.

[Examples 47 to 52 and Comparative Examples 10 to 1]
1] On a triacetyl cellulose film (thickness 100 μm, manufactured by Fuji Photo Film Co., Ltd.) coated with a gelatin thin film (0.1 μm), the following coating liquid containing polyvinyl alcohol shown in Table 4 described below was applied to a bar coater. And apply
It was heated and dried with hot air at 90 ° C. to form a polymer layer having a thickness of 0.8 μm. [Coating liquid] Polyvinyl alcohol shown in Table 4 1.0 part Water 18.0 parts Methanol 6.0 parts The surface of the obtained polymer layer was rubbed roll outer diameter: 8
0 mm, film transport speed: 100 m / min, rubbing roll rotation speed: 1000 rpm, and film transport tension: 1 kgf / cm
A rubbing process was performed under the conditions of substrate width to form an alignment film. A rubbing process was performed under bing conditions to form an alignment film. When the in-plane main refractive index is nx, ny, the refractive index in the thickness direction is nz, and the thickness is d, the triacetylcellulose film has | nx−ny | × d = 6 nm, {(nx
+ Ny) / 2-nz} d = 40 nm, which was almost negative uniaxial, and the optical axis was almost in the normal direction of the film.

(Layer of discotic liquid crystalline compound (optically anisotropic layer)
Formation of) a coating liquid for forming a discotic liquid crystalline compound layer having the following composition on the alignment film on the rubbing-treated film with a wire bar (# 3 bar is used) and dried, A coating layer of a discotic liquid crystalline compound was formed. [Coating liquid] Cellulose acetate butyrate 4 parts (CAB551-0.2, manufactured by Eastman Chemical Company) Discotic liquid crystal compound TP-3 182 parts Ethylene glycol modified totimethylol propane 18 parts Triacrylate (V # 360, Osaka Organic Chemical Co., Ltd.) Photopolymerization initiator 6 parts (Irgacure 907, Nippon Ciba Geigy Co., Ltd.) Sensitizer 2 parts (Kayacure-DETX, Nippon Kayaku Co., Ltd.) Methyl ethyl ketone 343 parts Film having this coating layer Was attached to a metal frame and heated for 3 minutes in a constant temperature bath at 120 ° C. to orient the discotic liquid crystal compound, and then UV irradiation for 1 second at 120 ° C. using a 120 W / cm high pressure mercury lamp. Then, by allowing to cool to room temperature, the thin film (optical Square layer, thickness 2 [mu] m) was formed to obtain an optical compensation sheet.

The optically anisotropic layers of the sheets obtained in Examples 47 to 52 and Comparative Examples 10 to 11 showed high transparency under crossed Nicols, and optical anisotropy was observed. Furthermore, regarding the obtained sheet, cellophane tape (adhesive tape)
Was used to evaluate the adhesiveness between the alignment film and the optically anisotropic layer. That is, a cellophane tape was attached to the surface of the optically anisotropic layer, and the tape was pulled and peeled in parallel with the optically anisotropic layer. And the adhesiveness was evaluated as follows. AA: No layer was attached to the surface of the peeled tape. CC: An optically anisotropic layer was attached to the surface of the peeled tape. Table 4 shows the results.

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[Table 4] Table 4 ──────────────────────────────────── Example Polymer layer Discotic Adhesion The polymer number, the compound number, ──────────────────────────────────── Example 47 No. 1 TP-3 AA Example 48 No. 39 TP-3 AA Example 49 No. 53 TP-3 AA Example 50 No. 1 / No. 39 = 1/1 TP-3 AA Example 51 No. 1 / No. 53 = 1/1 TP-3 AA Example 52 No. 39 / No. 53 = 1/1 TP-3 AA ──────────────────────────────────── Comparative Example 10 ^* MP -203 TP-3 CC Comparative Example 11 ^** PVA-117 TP-3 CC ───────────────────────────────── ──── Remarks: *, ** Made by Kuraray Co., Ltd.

The optical compensatory sheets of Examples 47 to 52 were prepared by coating an alignment film made of a polymer having a polymerizable group with an optically anisotropic layer made of a discotic liquid crystalline compound having a polymerizable group. It is made by curing. Therefore, these layers are strongly bonded. On the other hand, in the optical compensatory sheets of Comparative Examples 10 to 11, an optically anisotropic layer made of a discotic liquid crystalline compound having a polymerizable group is applied on an alignment film made of a polymer having no polymerizable group to form an optically anisotropic layer. It is made by curing only one layer. These layers are easily peeled off. Therefore, it was confirmed that the two layers of the optical compensation sheets of Examples 47 to 52 were chemically bonded to each other.

When the discotic liquid crystal compounds used in the above-mentioned examples are compared with the above-mentioned discotic morphological characteristics, when a = 1, b and c are 0.89 respectively.
And 0.29.

[0166]

The element comprising the transparent support of the present invention and the specific polymer layer provided thereon can be easily treated with a liquid crystal compound (particularly a discotic liquid crystal compound) by subjecting the polymer layer to an alignment treatment. It can be oriented.
Therefore, the above element is useful not only as an optical compensation sheet but also as a substrate of a liquid crystal cell. Further, in the optical compensation sheet of the present invention, the polymer of the alignment film and the liquid crystal compound of the optically anisotropic layer are chemically bonded at the interface between these layers. Therefore, the above-mentioned optical compensation sheet exhibits high adhesiveness between the alignment film and the optically anisotropic layer, so that it can be said that this sheet has excellent durability as well as a wide viewing angle. Further, the above optical compensation sheet is formed by applying an optically anisotropic layer made of a discotic compound having a polymerizable group onto an alignment film made of a specific polymer having a polymerizable group (eg, vinyl group), and forming these layers. Is prepared by applying UV light or heat. Thus, the elements of the present invention can be used to advantage in making the above sheets.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a typical structure of an element having a polymer layer of the present invention.

FIG. 2 is a sectional view showing a typical structure of an optical compensation sheet of the present invention.

FIG. 3 is a schematic view showing a typical structure of an optically anisotropic layer of the optical compensation sheet of the present invention.

FIG. 4 is a schematic view showing a typical structure of a liquid crystal display device having an optical compensation sheet of the present invention.

[Explanation of symbols]

11, 21, 31 Transparent support 12 Polymer layer 22, 32 Alignment film 23, 33 Optical anisotropic layer 34 Normal line of optical anisotropic layer A, B Polarizing plate PA Polarizing axis of polarizing plate PB Polarizing axis of polarizing plate B RF ₁ , RF ₂ optical compensation sheet BL backlight R ₁ optical compensation sheet RF ₁ rubbing direction R ₂ optical compensation sheet RF ₂ rubbing direction TNC liquid crystal cell

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08F 216/12 MLA C08F 216/12 MLA 216/14 MKZ 216/14 MKZ 216/38 MLC 216/38 MLC 218/04 MLH 218/04 MLH 218/10 MLJ 218/10 MLJ G02F 1/1337 G02F 1/1337 (31) Priority claim number Japanese Patent Application No. 7-210212 (32) Priority Sun 7 (1995) July 27th (33) Priority claiming country Japan (JP) (31) Priority claiming number Japanese Patent Application No. 7-247412 (32) Priority Day Hei 7 (1995) September 26 (33) Priority claiming country Japan (JP) )

Claims (13)

[Claims] 1. An optical compensation sheet comprising a transparent support, an alignment film made of a polymer, and an optically anisotropic layer made of a liquid crystalline compound in this order, and a polymer of the alignment film,
An optical compensatory sheet, which is chemically bonded to a liquid crystal compound of an optically anisotropic layer via an interface between these layers. 2. The optical compensation sheet according to claim 1, wherein the polymer of the alignment film is formed of polyvinyl alcohol in which at least one hydroxyl group is substituted with a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety. 3. The optical compensatory sheet according to claim 1, wherein the optically anisotropic layer is formed of a liquid crystal compound having a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety. 4. The optical compensatory sheet according to claim 1, wherein the liquid crystal compound in the optically anisotropic layer is a discotic liquid crystal compound having a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety. 5. A transparent support and a polymer layer provided thereon, wherein the polymer of the polymer layer has a vinyl, oxiranyl or aziridinyl moiety substituted with at least one hydroxyl group. An element having a polymer layer, characterized in that it comprises a polymerized polyvinyl alcohol. 6. The element according to claim 5, wherein the group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety is bonded to the polymer chain of the polyvinyl alcohol derivative through an ether bond, a urethane bond, an acetal bond or an ester bond. . 7. The element according to claim 5, wherein the group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety has no aromatic ring. 8. The polyvinyl alcohol has the following general formula (I): (However, L ¹¹ represents an ether bond, a urethane bond, an acetal bond or an ester bond; R ¹¹ represents an alkylene group or an alkyleneoxy group; L ¹² represents R
Represents a linking group connecting ¹¹ and Q ¹¹ ; Q ¹¹ is vinyl;
Represents oxiranyl or aziridinyl; x1 + y1
Under the condition of + z1 = 100, x1 is 10 to 99.9 mol%, y1 is 0.01 to 80 mol%, and z1 is 0 to 70.
Mol%; and k and h are 0 or 1 respectively.
The element of claim 5 represented by 9. An element comprising a transparent support, an alignment film made of a polymer, and an optically anisotropic layer made of a liquid crystalline compound in this order, wherein the polymer of the alignment film and the liquid crystalline compound of the optically anisotropic layer are included. Is an element having an alignment film characterized by being chemically bonded via the interface of these layers. 10. The polymer of the alignment film is a group having a vinyl moiety, an oxiranyl moiety or an aziridinyl moiety,
10. The element of claim 9 formed from polyvinyl alcohol having at least one hydroxyl group substituted. 11. An optical compensation sheet comprising a transparent support, an alignment film made of a polymer, and an optically anisotropic layer made of a liquid crystalline compound in this order, wherein the polymer of the alignment film is represented by the following general formula (II): : [Chemical 2] (However, R ²¹ represents an alkyl group, or an alkyl group substituted with alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy; W ²¹ represents an alkyl group, Alkyl, alkoxy,
Aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy substituted alkyl group, alkoxy group, or alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or Represents an alkoxy group substituted with crotonoyloxy; q is 0 or 1, and n is an integer of 0-4) consisting of polyvinyl alcohol substituted with at least one hydroxyl group. An optical compensation sheet characterized by: 12. A transparent support and a polymer layer provided thereon, wherein the polymer of the polymer layer has the following general formula (II): (However, R ²¹ represents an alkyl group, or an alkyl group substituted with alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy; W ²¹ represents an alkyl group, Alkyl, alkoxy,
Aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy substituted alkyl group, alkoxy group, or alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or Represents an alkoxy group substituted with crotonoyloxy; q is 0 or 1, and n is an integer of 0-4) consisting of polyvinyl alcohol substituted with at least one hydroxyl group. An element having a polymer layer characterized by: 13. In an element comprising a transparent support, an alignment film made of a polymer and an optically anisotropic layer made of a liquid crystalline compound in this order, the polymer of the alignment film is represented by the following general formula (II): Chemical 4] (However, R ²¹ represents an alkyl group, or an alkyl group substituted with alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy; W ²¹ represents an alkyl group, Alkyl, alkoxy,
Aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or crotonoyloxy substituted alkyl group, alkoxy group, or alkyl, alkoxy, aryl, halogen, vinyl, vinyloxy, oxiranyl, acryloyloxy, methacryloyloxy or Represents an alkoxy group substituted with crotonoyloxy; q is 0 or 1, and n is an integer of 0-4) consisting of polyvinyl alcohol substituted with at least one hydroxyl group. An element having an alignment film characterized by.